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PubMed1992

The use of mineral crystals as bio-markers in the search for life on Mars.

Photographs that depict presumed fluvial features on the martian surface have led geologists to hypothesize that water flowed across the early martian terrain. From this, it has been further hypothesized that the surface and atmospheric conditions on early Mars were similar to those on early Earth. Because the oldest fossil evidence of life on Earth dates back to this early period, at least 3.5 billion years ago, the possibility exists that the early Martian environment could have also been conducive to the origin of life. To investigate this possibility, universal signatures or bio-markers indicative of past (or present) biological activity must be identified for use in the search for life on Mars. Several potentially applicable biomarkers have been identified and include: organics (e.g., specific classes of lipids and hopanes), suites of specific inorganic and organic compounds, as well as the isotopic ratios of C, N, and S. Unfortunately, all of these bio-markers may be of biologic or abiotic origin; these origins are often difficult to distinguish. Thus, the discovery of any one of these compounds alone is not a bio-marker. Because minerals produced under biologic control have distinctive crystallographies, morphologies, and isotopic ratios that distinguishable from abiotically produced minerals with the same chemical composition, and are stable through geologic time, we propose the use of minerals resulting from biologically controlled mineralization processes as bio-markers.

Atmosphere↗
PubMed1991

Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters.

A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO2 evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1-5 micromoles of carbon and has an associated blank of 0.1-0.2 micromole of carbon. Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO2 as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3%. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The delta 13C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC. The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average delta 13C = -12.4%). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and delta 13C of pore-water DOC was nearly 8% lighter at 1.5-2.0-cm depth than in the mat surface layer (0-0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and delta 13C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.

Carbon↗
PubMed1990

Intact capture of hypervelocity projectiles.

The ability to capture projectiles intact at hypervelocities opens new applications in science and technology that would either not be possible or would be very costly by other means. This capability has been demonstrated in the laboratory for aluminum projectiles of 1.6 mm diameter, captured at 6 km/s, in one unmelted piece, and retaining up to 95% of the original mass. Furthermore, capture was accomplished passively using microcellular underdense polymer foam. Another advantage of capturing projectiles in an underdense medium is the ability of such a medium to preserve a record of the projectile's original velocity components of speed and direction. A survey of these experimental results is described in terms of a dozen parameters which characterize the amount of capture and the effect on the projectile due to different capture media.

Acrylic Resins↗
PubMed1990

Continuous monitoring of a changing sample by multiplex gas chromatography.

Multiplex gas chromatography (MGC) is a technique in which multiple samples may be introduced into a chromatographic system regardless of the elution time of the individual components. Although the output obtained from a MGC experiment is not directly interpretable, computational techniques can be used to obtain the chromatogram from the detector output data. This is done by calculating the impulse response function from the multiplexed output data.

Butanes↗
PubMed1995

Life on Mars? I. The chemical environment.

The origin of life at its abiotic evolutionary stage, requires a combination of constituents and environmental conditions that enable the synthesis of complex replicating macromolecules from simpler monomeric molecules. It is very likely that the early stages of this evolutionary process have been spontaneous, rapid and widespread on the surface of the primitive Earth, resulting in the formation of quite sophisticated living organisms within less than a billion years. To what extent did such conditions prevail on Mars? Two companion-papers (Life on Mars? I and II) will review and discuss the available information related to the chemical, physical and environmental conditions on Mars and assess it from the perspective of potential exobiological evolution.

Earth, Planet↗
PubMed1995

Life on Mars? II. Physical restrictions.

The primary physical factors important to life's evolution on a planet include its temperature, pressure and radiation regimes. Temperature and pressure regulate the presence and duration of liquid water on the surface of Mars. The prolonged presence of liquid water is essential for the evolution and sustained presence of life on a planet. It has been postulated that Mars has always been a cold dry planet; it has also been postulated that early mars possessed a dense atmosphere of CO2 (> or = 1 bar) and sufficient water to cut large channels across its surface. The degree to which either of these postulates is true correlates with the suitability of Mars for life's evolution. Although radiation can destroy living systems, the high fluxes of UV radiation on the martian surface do not necessarily stop the origin and early evolution of life. The probability for life to have arisen and evolved to a significant degree on Mars, based on the postulated ranges of early martian physical factors, is almost solely related to the probability of liquid water existing on the planet for at least hundreds of millions to billions of years.

Atmospheric Pressure↗
PubMed1995

Search for life on Mars: evaluation of techniques.

An important question for exobiology is, did life evolve on Mars? To answer this question, experiments must be conducted on the martian surface. Given current mission constraints on mass, power, and volume, these experiments can only be performed using proposed analytical techniques such as: electron microscopy, X-ray fluorescence, X-ray diffraction, alpha-proton backscatter, gamma-ray spectrometry, differential thermal analysis, differential scanning calorimetry, pyrolysis gas chromatography, mass spectrometry, and specific element detectors. Using prepared test samples consisting of 1% organic matter (bovine serum albumin) in palagonite and a mixture of palagonite, clays, iron oxides, and evaporites, it was determined that a combination of X-ray diffraction and differential thermal analysis coupled with gas chromatography provides the best insight into the chemistry, mineralogy, and geological history of the samples.

Aluminum Silicates↗
PubMed1995

A "cryptic" microbial mat: a new model ecosystem for extant life on Mars.

If life were present on Mars to day, it would face potentially lethal environmental conditions such as a lack of water, frigid temperatures, ultraviolet radiation, and soil oxidants. In addition, the Viking missions did not detect near-surface organic carbon available for assimilation. Autotrophic organisms that lived under a protective layer of sand or gravel would be able to circumvent the ultraviolet radiation and lack of fixed carbon. Two terrestrial photosynthetic near-surface microbial communities have been identified, one in the inter- and supertidal of Laguna Ojo de Liebre (Baja California Sur, Mexico) and one in the acidic gravel near several small geysers in Yellowstone National Park (Wyoming, U.S.A.). Both communities have been studied with respect to their ability to fix carbon under different conditions, including elevated levels of inorganic carbon. Although these sand communities have not been exposed to the entire suite of Martian environmental conditions simultaneously, such communities can provide a useful model ecosystem for a potential extant Martian biota.

Animals↗
PubMed1995

Surface-atmosphere interactions on Titan compared with those on the pre-biotic Earth.

The surface and atmosphere of Titan constitute a system which is potentially as complex as that of the Earth, with the possibility of precipitation, surface erosion due to liquids, chemistry in large surface or subsurface hydrocarbon reservoirs, surface expressions of internal activity, and occasional major impacts leading to crustal melting. While none of the above have been observed as yet, the composition, density and thermal properties of Titan's atmosphere make it uniquely suited in the outer solar system as a place where such processes may occur. The one attribute of the Earth not expected on Titan is biological activity, which has had a profound effect on the evolution of the Earth's surface-atmosphere system. The earliest environment of Titan could have been warm enough for liquid ammonia-water solutions to exist on or near surface; pre-biotic organic processes may have taken place in such an environment. After a few hundred million years surface ammonia-water would have disappeared. Therefore, study of Titan through the Cassini-Huygens mission, planned for launch in 1997, primarily affords the opportunity to understand planet-wide surface-atmosphere interactions in the presence of fluids but in the absence of life. More speculative is the possibility that endogenic and exogenic heating continue to provide short-lived environments on Titan wherein pre-biotic organic processes in the presence of water happen.

Atmosphere↗
PubMed1995

Very low temperature formaldehyde reactions and the build-up of organic molecules in comets and interstellar ices.

We have investigated thermally promoted reactions of formaldehyde (H2CO) in very low temperature ices. No such reactions occurred in ices of pure formaldehyde. However, addition of trace amounts of ammonia (NH3) were sufficient to catalyze reactions at temperatures as low as 40 K. Similar reactions could take place in interstellar ices and in Comets and produce considerable amounts of organic molecules.

Ammonia↗
PubMed1995

Polycyclic aromatic hydrocarbon ions and the diffuse interstellar bands.

Neutral naphthalene (C10H8), phenanthrene (C14H10), and pyrene (C16H10) absorb strongly in the ultraviolet and may contribute to the extinction curve. High abundances are required to produce detectable structures. The cations of these PAHs absorb in the visible. C10H8+ has 12 discrete absorption bands which fall between 6800 and 5000 angstroms. The strongest band at 6741 angstroms falls close to the weak 6742 angstroms diffuse interstellar band (DIB). Five other weaker bands also match DIBs. The possibility that C10H8+ is responsible for some of the DIBs can be tested by searching for new DIBs at 6520, 6151, and 5965 angstroms, other moderately strong naphthalene cation band positions. If C10H8+ is indeed responsible for the 6742 angstroms feature, it accounts for 0.3% of the cosmic carbon. The spectrum of C16H10+ is dominated by a strong band at 4435 angstroms in an Ar matrix and 4395 angstroms in a Ne matrix, a position which falls very close to the strongest DIB, that at 4430 angstroms. If C16H10+, or a closely related pyrene-like ion is indeed responsible for the 4430 angstroms feature, it accounts for 0.2% of the cosmic carbon. We also report an intense, very broad UV-to-visible continuum which is associated with both ions and could explain how PAHs convert interstellar UV and visible radiation into IR.

Argon↗
PubMed1991

Determination of C1-C4 alkanes by ion mobility spectrometry.

Flight instrumentation for the analyses of extraterrestrial environments must often perform under severely restricted conditions. Often, the detection and identification of a multitude of chemical species is required to fulfill the scientific objectives of the mission. It is therefore important that the analytical instrumentation have universal response. The gas chromatograph-ion mobility spectrometer (GC-IMS) has the potential to provide the sample separation, identification and sensitivity necessary for a successful analysis. However, the IMS has poor sensitivity for the C1-C4 alkanes. The abundance of these molecules at various extraterrestrial sites is often of great importance to exobiologists. This study focuses on optimizing IMS sample ionization mechanisms for the C1-C4 alkanes and other hydrocarbons of interest to exobiology.

Alkanes↗
PubMed1992

Extraction technique for the determination of oxygen-18 in water using preevacuated glass vials.

The need for a rapid, inexpensive technique for routine 18O/16O extraction from water has arisen recently through applications in the medical sciences and in hydrology. The traditional experimental technique for determining the oxygen isotope composition of water, the CO2-H2O equilibration method, is tedious, time consuming, and involves the use of custom-made glass apparatus. Furthermore, because of potential memory effects from one sample to the next, the glassware needs to be thoroughly cleaned between runs. A few attempts have been made to improve upon the method. Attempts to analyze water directly in the source of the mass spectrometer produced large memory effects and questionable results. Commercially available apparatus for automated extraction of 18O/16O from water is generally prohibitively expensive and often is designed to interface only with the manufacturer's own mass spectrometer. The method described in this paper utilizes inexpensive, off-the-shelf, preevacuated, glass vials. Preevacuated vials have been used by others for the isotopic analysis of breath CO2 and are well tested. The vials can be purchased in bulk from scientific apparatus suppliers at a relatively low cost. These are coupled with a simplified extraction line consisting of a stainless steel syringe needle and a glass cold trap. Vials are filled with CO2 and H2O and shaken in a constant-temperature water bath for at least 90 min. Since the vials are discarded after use, no cleaning is necessary, essentially eliminating any memory effect. Reproducibility is generally better than +/- 0.05%. The only reagents required are gaseous CO2 for equilibration, a dry ice/alcohol mixture for trapping water, and liquid nitrogen for transferring the CO2.

Carbon Dioxide↗
PubMed1995

Infrared spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. 2. The members of the thermodynamically most favorable series through coronene.

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHs) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene:phenanthrene, pyrene, benzo[e]pyrene, benzo[ghi]perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d10, and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Astronomical Phenomena↗
PubMed1987

Molecular dynamics of the water liquid-vapor interface.

The results of molecular dynamics calculations on the equilibrium interface between liquid water and its vapor at 325 K are presented. For the TIP4P model of water intermolecular pair potentials, the average surface dipole density points from the vapor to the liquid. The most common orientations of water molecules have the C2 nu molecular axis roughly parallel to the interface. The distributions are quite broad and therefore compatible with the intermolecular correlations characteristic of bulk liquid water. All near-neighbor pairs in the outermost interfacial layers are hydrogen bonded according to the common definition adopted here. The orientational preferences of water molecules near a free surface differ from those near rigidly planar walls which can be interpreted in terms of patterns found in hexagonal ice 1. The mean electric field in the interfacial region is parallel to the mean polarization which indicates that attention cannot be limited to dipolar charge distributions in macroscopic descriptions of the electrical properties of this interface. The value of the surface tension obtained is 132 +/- 46 dyn/cm, significantly different from the value for experimental water of 68 dyn/cm at 325 K.

Chemical Phenomena↗
PubMed1989

The case for planetary sample return missions. 2. History of Mars.

Principal science goals for exploration of Mars are to establish the chemical, isotopic, and physical state of Martian material, the nature of major surface-forming processes and their time scales, and the past and present biological potential of the planet. Many of those goals can only be met by detailed analyses of atmospheric gases and carefully selected samples of fresh rocks, weathered rocks, soils, sediments, and ices. The high-fidelity mineral separations, complex chemical treatments, and ultrasensitive instrument systems required for key measurements, as well as the need to adapt analytical strategies to unanticipated results, point to Earth-based laboratory analyses on returned Martian samples as the best means for meeting the stated objectives.

Chemical Phenomena↗
PubMed1992

Time resolved simulation of lightning by lip.

In this letter, we report results of time resolved spectra of lightning simulation in air by laser-induced plasma (LIP). The measured electron temperatures varied from (1.7 +/- 0.1)X10(4) K at 600 ns to (1.2 +/- 0.1)X10(4)K at 4 microseconds after the ignition of the plasma. Electron densities in the plasma varied from (7.0 +/- 1.4)X10(17)/cm3 to (9.0 +/- 1.8)X10(16)/cm3 for the above times. We also present, for the first time, a comparison of state variables for LIP and natural lightning. We find that immediately following the ignition both natural lightning and LIP reach temperatures in excess of 16,000K and relax to ambient pressure with different rates. They are expected to approach 2000 - 4000 K temperature range, which is important to chemical synthesis, in an asymptotically similar fashion.

Electrons↗
PubMed1991

Particulate organic matter delta 13C variations across the Drake Passage.

A 7 % gradient in the delta 13C of suspended particulate organic matter (POM) was observed in samples taken during two transects across the Drake Passage during March 1986. This POM delta 13C transition from -23.2 % at 53.3 degrees S to values as low as -30.3 % at > 62 degrees S does not track previously reported abrupt changes in water chemistry and plankton species composition associated with the Polar Front Zone that resides at approximately 58 degrees S in this region. Also, the north-south isotopic trend is not accompanied by significant changes in POM carbon or nitrogen concentrations, or in POM C/N. Differences in plankton standing crop or biochemistry (e.g., lipid content) therefore do not appear responsible for the isotopic trends observed. The latitudinal change in POM delta 13C is, however, highly correlated with water temperature and with the calculated concentration of CO2 (aq) at equilibrium with atmospheric CO2. These observations are consistent with the hypothesis that [CO2 (aq)] significantly influences POM delta 13C in ocean surface waters.

Animals↗